Manufacture of chromed complexes of azo and ortho-hydroxy-azo dyestuffs



Patented Sept. 29, .1931

UNITED, STATES HENRY MmocoUR'r, or SOTTEVILLE-LEZ-BOUEN,iFIfiAiICE,nssreiionfmo oofijgeen in NATIONALE DE MATIERES ooLoRANTEs ETMANUFAc'rUn-Es 13E rnonul rs can/[muss nu NORD REUNIES,ErABLIssEnnn'rsxUnLnann, or years, marten;

A CORPORATION OF manor:

MANUFACTURE or cnnoivrnncomrmxnsoe jaizo an osmemsoxinzb "nynsrurrsf NoDrawing. Application filed August 20, 1923, Serial No. aoomamid-infisherman $1528.

This invention relates to the manufac-' ture of chromed complexes of'azo and orthooxy-a-zo dyestufis. I v

The chromed complex'es of azo and orthohydroxy-azo dyestufl's have beenprepared up to the present time byreacting upon SiLld' dyestuffs withmineral salts of chromium such as the halogen compounds of chromium andin particular chromium fluoride, in the presence of agents for theabsorption of the sulfonic acids of aromaticcarbides such as benzene andits homologues or naphthalene and their substituted derivatives favor,

in a very pronounced manner the formation of chromed complexes of am andortho-hydroxy-azo dyestuffs.

The new products obtained by means of these chromium salts are for themost part very pure. They are often crystalline and give much brighterdyeing'than the corre sponding products obtained by other processes andfurther they possess great lasting properties. They can be appliedinwlogues, naphthalene, etc.) and solutions of chromium sulphate Example 128 kgs. of the sodium salt of the azoic compound4-hydroxy-benzene-l-azo-salicylic acid (obtained from diazotizedp-aminosalicylic acid and phenol) arefheated' under reflux for about 8'h0urswith400 litres o a solutionof chromium benze'n'e-monosul phon'ate(containing 10 kilos Cr OQL-"E y The complex obtained is transformedinto" its sodium salt which dyes wool-inan'5acid bath in' greenishyellowshades of'great pur it very f t-to fulling and'light} 39,4-kgs5 ofthemono-sodium salt of the dyestufl resulting from the couplingaof thdiazocompound 0f"1-naphthylami ne 4 s 'l phonic acidwith salicylicacidareiheate under-reflux with 400 litres of a solutio' of chromium1.5-naphthalene disiilphon'ate (containing 10 kilos C130 lTh'e tr'ansformationis complete in two hours: Aft' treatment with sodium acetate 'thesbdiumf salt of the chromed complex is isolatedby saltingout. 1 T

The product obtained gives on wool-brigh reddish yellow dyeings.

34 of, the free'acid of thei yestufig resulting from thecombin'ation of-th edi azo derivative of l-amino-Z naphthol 4-sulphoi1io'--E acid and"1'-phenyl-3 methyl-Efipyrazolone are heated in a leaded autoclave for10 hours at 130 C. with 400 litres of a solution of chromium1.5-naphthalene disulphonate (containing 10 kilos Cr O 'At the end ofthis time the transformatit-on is complete and the free acid of the newchromedcomplex separates in'small crystals which have a metallic greenreflex.' Transformed into the sodium salt it, dyes wool in an acidbathin bright rose shades while the corresponding product obtained bymeans of chromium formate, for example, gives only a dull bluish red.

. Example 4 kgs.- of the mono-sodium salt of the dyestuff obtained bymeans of the diazo derivative of 1-amino-2-naphthol t-sulphonic acid and1.8-naphthol mono sulphonic acid are heated under reflux with 500 litresof a solution of chromium 1.5-naphthalened1sulphonate (containing 12.5kilos Cr O At the end of two hours the transformation is completeg thewhole; is :allowed to cook; (the? chrome iTconrplem separates i-"in-zsmail bronze crystals resembling those of methyleneiblue;

' The new complex obtained dyes wool in V gi 'eenis'lfbhie shades" ofgreat purity; and ex ceHnti fastnessto light: g g V '1 The "analogous"compounds of the same 10 diazotized acid with or and ,B-naphthol areeasily transformeirintoa chromed complexess by treatment during siizhours in anautor.

clave at 120 C. with the solution of chrom -b z n me lph t g a:

'15 g Emampleb' 49'5kgszaof 1 the: monossodiumn salt t of "Ethecompound; ohtaineet bya th'e action oi thB f dialer-5: COIIIQOLH'ICLr of5=n-itree2-amin0-l+hy-, droxy-benzenn andm 12naphthy1 amine-5fi -cl-i-.'

sulp bonicnacid are? heated iclaliri-ng; 101-to--. '12honrssunderrreflux with 500-flitres-ofi (a solu-- tiomof ichrominmz'alfimphthalenedisulpho; nate (containing-312.5kilosGr'gOg)2- .7 At the endof this .time the whole is al-' lowed to cool. Thechrome'd compoundseparates in the form}:ofaarcq stalline :powcler; appearing; reddish byrrefieetcd f'light It? dyesawoolfiim van :Jacicla bath rintabluishfigreen; ;sha'desl.r which "are very? pure Whereas thec'compound-l obtaineel;.-by means oi chromium: rfomnateegiyesanuch'gellowerishadesa- Byg'emplogying chromium: benzene disulaphonnte andflchromiumfnaphthalene:trisirb? A aphonate analngousrresultszarecbtainetla miltzliclfiili hlsi r v I 1 Process for the manufactureof chromedi complexes@ 0% .azo -anda ortho-hydnexywazo' dyestuffs bytreating the-edyestuifi withaaa 40 {chromium salt of an aromaticsulphonic acid of the group consisting of'benzene andnaphthalenevmonoeand poLysul-phonic Im-ztstimony; whereofv :Ishavessignedcthisa pecifications. 7 7 l mnn cmnoeoem

